JP3268104B2 - Photographic elements that provide improved color rendering - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to color photographic elements and processes that provide improved color rendering.

[0002]

BACKGROUND OF THE INVENTION It is desirable to improve the color rendering of photographic elements. In particular, it is desirable to have the ability to suppress the red-sensitive layer and the blue-sensitive layer to the extent desired for the green layer developing action. One method of improving color rendering is to use couplers described in U.S. Pat. Nos. 4,163,670, 2,428,054, and 3,148,052. . However, when this color correction method is used, the unexposed area is strongly colored, and the printing time is prolonged. Furthermore, in multilayer structures where the layer arrangement is blue-sensitive, green-sensitive, and red-sensitive, only yellow colored couplers can be used in the green-sensitive layer for exposure. That is, the red layer sensitivity decreases.

[0003] CRBarr, JR Thirtle, and PWVittum
Photographic Science and Engineering, Vol. 13, 74
"DIR" couplers or "development inhibitor releasing couplers" as defined in N, 80 214-217 (1969) are known to produce an interlayer effect and to release inhibitor fragments imagewise to improve color reproduction. It is generally known. In general, there are two types of inhibitor fragments. An inhibitor fragment (strong inhibitor) that strongly adsorbs to silver and suppresses development widely, and an inhibitor fragment (weak inhibitor) that weakly adsorbs to silver and suppresses development to a lesser extent. Both types of inhibitor fragments can be attached to the coupler via a timing group that diffuses the inhibitor precursor. However, DIRs that bind to the pyrazolone nucleus via a timing group are unsuitable and costly to manufacture. Accordingly, there is a need for a DIR compound in a green-sensitive layer that overcomes the problems.

[0004] A number of attempts have been made to reveal layer sequences incorporating various types of DIRs. For example,
U.S. Pat. No. 4,804,619 discloses the use of a diffusible DIR for a most sensitive green-sensitive layer of a specified layer thickness. Due to its weak inhibitory ability, inhibitor fragments released from the DIR can become diffusible,
Alternatively, they can be linked via a timing group to be diffused. However, no particular combination of DIRs used in the high and lower speed layers is disclosed at all.

US Pat. No. 4,414,308 teaches the inclusion of a DIR with a timing group in the fast layer, the slow layer and / or the middle insensitive layer of a multilayer pack. No specific layer arrangement or DIR combination is suggested. US patents using DIR in multi-layer applications are: US Pat.
Nos. 963,465, 4,145,219 and 4,2
Nos. 73,861, 4,670,375 and 4,
564,587. None of the described arrangements provide the desired effect of green light in the red and blue records to sufficiently improve color rendering.

[0006]

The incorporation of the specified combination of DIRs therefore provides improved color rendering due to the ability to suppress the red and blue sensitive layers to the desired degree as a green layer developing action. Providing color photographic elements and processing is a problem to be solved.

[0007]

SUMMARY OF THE INVENTION A photographic element and its associated effective processing comprises at least two light-sensitive silver halide layers sensitized to green light and having different sensitivities, comprising a light-sensitive layer and a light-sensitive layer. A timing group comprising a yellow dye-forming DIR coupler releasing a development inhibitor having a weak inhibitor fragment associated therewith, and containing a strong inhibitor fragment releasing a precursor of the development inhibitor fragment associated with the insensitive layer Dye formation D having
It further comprises an IR coupler.

This layer arrangement provides the ability to suppress the red and blue sensitive layers to the extent desired for the green layer developing action, thereby providing improved color rendering.

[0009]

DETAILED DESCRIPTION OF THE INVENTION A photographic element of the present invention comprises a sensitive green sensitive layer containing a yellow dye forming development inhibitor releasing (DIR) coupler releasing a weak inhibitor, and a cyan dye having a timing group releasing a strong inhibitor. Comprising a slow green sensitive layer containing the resulting DIR coupler. Couplers with weak inhibitor fragments produce yellow dyes when coupled. The coupler has the effect of offsetting the inhibitory effect of the inhibitor in the blue-sensitive layer. Therefore, the effect of suppressing the generation of yellow dye in the blue-sensitive layer is offset by increasing the generation of yellow dye in the green-sensitive layer. The fact that the inhibitor is weak is effective in minimizing the inhibitory effect of the green-sensitive layer from which DIR is released, and this helps to minimize the opposite effect on green sensitivity.

[0010] Similarly, couplers having a strong inhibitor with a timing group produce a cyan dye when coupled. The cyan dye helps to counteract the suppression of cyan dye formation in the red-sensitive layer as a result of releasing the inhibitor in the green-sensitive layer. The presence of the timing group together with the strong inhibitor helps to minimize the inhibitory effect in the green-sensitive layer, which is itself released as an uninhibited precursor. This precursor is therefore free to move from the layer from which it was released.

Couplers which react with oxidized color developing agents to form cyan dyes are disclosed in US Pat. No. 2,772,162.
No. 2,895,826, 3,002,836
Nos. 3,034,892 and 2,474,293
No. 2,423,730, 2,367,531
Nos. 3,041,236 and 4,883,746, and "Farbkupplereine Literaturubersich"
t '', published by Agfa Mitteilungen, Band III, pp. 156-175 (1
961), and other typical patent specifications and publications. Preferably, such couplers are phenols and naphthols which react with oxidized color developing agents to form cyan dyes.

Couplers which react with oxidized color developing agents to form magenta dyes are disclosed in US Pat. No. 2,600,7
No. 88, No. 2,369,489, No. 2,343,70
No. 3, 2, 311, 082, 3, 152, 896
No. 3,159,429 and 3,062,653
No. 2,908,573 and "Farbkupple
reine Literaturubersicht, published by Agfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably,
Such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that react with oxidized color developing agents to form magenta dyes.

Couplers which react with oxidized color developing agents to form yellow dyes are described in US Pat. No. 2,875,0
No.57, No.2,407,210, No.3,265,50
No. 6, 2,298,443 and 3,048,194
No. 3,447,928 and "Farbkupplere
ine Literaturubersicht, published by Agfa Mitteilungen, B
and III, pp. 112-126 (1961), and are described in representative patent specifications and publications. Such couplers are typically open chain ketomethylene compounds.

[0014] Methods for evaluating the inhibitory strength of inhibitor releasing couplers are well known in the art. See U.S. Pat. No. 5,006,448. In the present invention, I.I. S. DIRs containing inhibitor fragments with a value of 50 or greater are classified as strong inhibitors, and those with values less than 50 are classified as weak inhibitors. Generally, during processing of an exposed photographic element, development inhibitors are released imagewise from the incorporated DIR compound. To evaluate the inherent inhibitory strength of such inhibitors, DIR
Independent release, using an invitation test. This test involves incubating exposed pieces of film with a solution having a given concentration of free inhibitor to be tested.
(imbibing). Burst nitrogen agitation of the inviving solution improves the reproducibility and efficacy of inhibitor incorporation. The measured intensity obtained by this test serves as an important guide in selecting inhibitors to improve the desired photographic acutance and color rendering.

A film sample to be subjected to the inhibition test of the inhibitor is shown below in a layer structure and a silver bromoiodide emulsion containing 6.4 mol% iodine.
² , silver halide: silver equivalent): overcoat: gelatin-2691 bis (vinylsulfonylmethyl) ether hardener-1.75% by weight of total gelatin cyan layer: gelatin-2691 green Sensitized AgBrI-1615 cyan dye-forming coupler (C-1) -753 Film support: poly (ethylene terephthalate)

[0016]

Embedded image

A piece of film cut from the coated element was tested with a density graduated test subject and Kodak Wratte.
Exposure was through a 99 (green) filter. The test piece before the development, carbonate buffer of pH 10, 5 × 10 in dimethylformamide 0.1% ^- in each separate pre-bath containing ⁵ molar concentration of the test inhibitor, nitrogen with stirring 38 ° C. And soaked. As controls, each test set consisted of a check specimen immersed in a pre-bath containing no inhibitor and a comparative inhibitor phenylmercaptotetrazole (CI-
1) and ethyl mercaptotetrazole (CI-2)
The test piece was immersed in a preliminary bath containing Photographic processing was performed at 38 ° C. in the following steps. Inhibitor preliminary bath 2 minutes Development (1) 2.75 minutes Stop 2 minutes Rinse 2 minutes Bleach 2 minutes Rinse 2 minutes Fix 2 minutes Rinse 2 minutes (1) The developer used in the test is as follows.

Developer g / l K ₂ SO ₃ 2.0 4-amino-3-methyl-N-ethyl-β-hydroxyethylaniline sulfate 3.35 K ₂ CO ₃ 30.0 KBr 1.25 KI 0 Adjust the pH to 10.0.

A red light densitometry curve was plotted for each specimen and the exposure step was selected when the check specimen without inhibitor showed a density of 1.0 on the fog. At the same point, the concentration of each test piece was recorded and the inhibitor strength number (IS No.) was calculated by the following formula: Was calculated.

For a given inhibitor I.I. S. Higher values result in stronger suppression, resulting in little dye density. Preferred weak inhibitors of the present invention are benzotriazoles and alkylmercaptotetrazoles. Table I shows examples of typical weak inhibitors and their corresponding I.V. S. Indicates a numerical value.

[0021]

[Table 1]

The strong inhibitors of the present invention are preferably aryl and arylalkyl mercaptotetrazoles and oxadiazoles. Suitable examples of strong inhibitors and their corresponding I.V. S. The numerical values are shown in Table II.

[0023]

[Table 2]

Additional examples of DIRs with weak and strong inhibitor groups are provided, for example, in US Pat. No. 5,006,448. The DIR in the less sensitive green layer of the present invention contains a timing group in addition to the strong inhibitor. The timing group attaches to the coupler component at any position to which the group released from the coupler by reaction with the oxidized color developing agent can attach. Preferably, the timing group is attached to the coupling position of the coupler component such that the timing group is displaced when reacting the coupler with an oxidized color developing agent. However, the timing group, as a result of the reaction of the coupler with the oxidized color developing agent,
It can be attached to a non-coupling position of the coupler component to be substituted. If the timing group is in a non-coupling position of the coupler component, the other groups can be in the coupling position and can be a normal coupling-off group or the same or different inhibitor fragments or precursors described in the present invention. Is included. Alternatively, the coupler component can have a timing group at each of the coupling and non-coupling positions. Therefore, the coupler of the present invention contains 1 mole per 1 mole of the coupler.
More than one mole of inhibitor or other photographically useful substance can be released. These released fragments can be the same or different and can be released at the same or different timings and rates.

The timing group can be any organic group that is effective to attach the coupler to the inhibitor fragment or precursor component, and after splitting off the coupler,
Preferably, for example, by an intermolecular nucleophilic substitution reaction of the type described in US Pat. No. 4,248,962.
Alternatively, for example, electron transfer along a conjugated chain (quinone-methide type) described in US Pat. No. 4,409,323.
(The disclosure of which is incorporated herein by reference) separates from the inhibitor component. Timing groups using a mechanism with electron transfer along the conjugated chain are particularly preferred. U.S. Pat. Nos. 4,842,994 and 5,135,839 contain a detailed description of suitable timing groups for use in the present invention.

The "intermolecular nucleophilic substitution reaction" is a reaction in which a nucleophilic center of a compound reacts directly or indirectly with an intermediary molecule at another place (an electrophilic center) of the compound to form an electrophilic center. A reaction that gives the effect of substituting a bonding group or atom. Such compounds have nucleophilic and electrophilic groups that are spatially related by the composition of the molecule and facilitate the approach of reactivity. Preferably, the nucleophilic and electrophilic groups can be readily formed by an intermolecular reaction in which a cyclic or excessive cyclic organic ring requires a nucleophilic center and an electrophilic center. And so on.

Useful actual classes of timing groups (T)
Is represented by the following structure:-(Nu-XE)-. Wherein Nu is a nucleophilic group attached to the position of the coupler that displaces during the reaction of the coupler with the oxidized color developing agent, and E is an electrophilic group attached to the described inhibitor fragment. Thus, after Nu has been displaced from the coupler, it can be displaced therefrom by Nu, and X is a linking group spatially related to Nu and E, wherein when displacing Nu from the coupler, 3-membered to 7-membered.
An intermolecular nucleophilic substitution reaction is carried out by forming a member ring (preferably 5 or 6 members).

A nucleophilic group (Nu) is understood to be an aggregate of atoms, one of which is electron rich. This atom is called the nucleophilic center. An electrophilic group (E) is understood to be an aggregate of atoms, one of which is electron deficient.
This atom is called the electrophilic center. In the photographic couplers described, the timing groups are separated from each other by a linking group such that upon release from the coupler component, the nucleophilic and electrophilic centers react to displace the inhibitor component from the timing group. And nucleophilic and electrophilic groups that are closely related. Until released from the coupler component,
The nucleophilic center may be protected from reaction with the electrophilic center, and the electrophilic center may be resistant to external attacks, such as hydrolysis.

At the nucleophilic center or at an atom associated with the nucleophilic center, the coupling of the coupler component to the timing group can prevent premature reaction, so that the timing group and the inhibitor from the coupler component can be prevented. Cleavage of the component can unblock the electrophilic center and react with the electrophilic center. Alternatively, premature reactions can be prevented by placing nucleophilic and electrophilic groups to protect them from reactive access until release. Timing groups can include additional substituents, for example, photographically useful groups, or their precursors (either bound to or released from the timing group).

A typical Nu group has an electron rich oxygen, sulfur and nitrogen atom. Representative E groups have electron-deficient carbonyl, thiocarbonyl, phosphonyl and thiophosphonyl moieties. Other useful Nu and E groups will be apparent to those skilled in the art. Particularly preferred are:
It is a timing group with the following structure:

[0031]

Embedded image

In the formula, X is selected from hydrogen or hydroxy, cyano, fluoro, chloro, bromo, iodo, nitro, alkyl, alkoxy, aryl, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carbonamide and sulfonamide, respectively. One or more substituents and Q is -N = or-
C (W) =, where W is a sigma greater than 0
Para (Hansch and Leo's Journal of Medicinal Che
mistry , 16 , 1207, (1973)). Typical W _{groups, -NO 2, -NHSO 2 CH 3} , -NH
_{SO 2 C 16 H 33, -NHCOCH} 3, -NHCOC 11 H
_{23, -Cl, -Br, -OCH 3} , -OCH 2 CH 2 O
CH ₃ , and so on. Other useful timing groups are described in U.S. Patent Nos. 4,737,451 and 4,546,073.
No. 4,564,587, 4,618,571,
No. 4,698,297 and European Patent Application Publication No. 16
7,168, 255,085 and 362,8
No. 70 is described in each specification.

The timing group comprises a component capable of controlling one or more reaction rates of the coupler with the oxidized color developing agent (diffusion rate of the inhibitor fragment released once from the coupler, and release rate of the inhibitor); It has a substituent. The timing groups can have additional groups, such as additional photographically useful groups, and can be kept attached to the timing groups and released individually. The timing group can have a ballast group.

In a preferred embodiment of the invention, the one or more green-sensitive layers comprises a yellow colored magenta dye-forming masking coupler. Any known coupler can be used for this purpose. The use of 4-arylazopyrazolone masking couplers is known in the art. For example, U.S. Pat.
5,170, 2,428,034, 2,80
8,329, 2,434,272, 2,70
Nos. 4,711, 2,688,539, 3,79
6,574, 3,476,560 and 4,42
7,763, EP 213,490 and U.S. Pat. No. 4,777,123 and Research.
Disclosure , VII, Part G December 1989, (Kenneth Maso
n Publication Ltd., Dudley Annex, 12a North Stree
, Emsworth, Hampshire PO10 7DQ, published by England). These are proven to be useful because they are colored yellow in unexposed areas and magenta in exposed areas. Thus, although the magenta dye produced in the color negative photographic process has a small but significant undesirable absorption in the blue region, this is due to the conversion of the mask color from yellow to magenta in the exposed regions, resulting in a blue absorption. Due to the relative reduction, it is possible to balance somewhat. The unwanted blue that can be adjusted to the spectral power of the light used, can produce a positive from the negative, and is essentially constant over both exposed and unexposed areas of the negative area Absorption can be effectively removed.

The following are examples of suitable masking couplers in addition to the MM-1 used in this example and considered identical at the end of this example:

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

The present invention is used in a two-layer green-sensitive pack and has an advantageous effect on color rendering, but the best results can be obtained in a three-layer green-sensitive pack or "triple coating". In this case, a weak inhibitor DIR is added to the highly sensitive green-sensitive layer.
It is preferable to use a strong inhibitor DIR having a timing group in the middle sensitivity layer. The materials of the present invention can be used in any of the methods and combinations when such materials are used in the field of photographic technology. Typically,
They are incorporated into a silver halide emulsion and the emulsion coated on a support to form part of a photographic element. Or,
They can be incorporated at a location adjacent to the silver halide emulsion layer that reacts during development in combination with a development product such as an oxidized color developing agent. That is, as used herein, the term "combined" means that the compound is in the silver halide emulsion layer or an adjacent layer and is capable of reacting with the silver halide development product during processing.

In order to control the movement of various compositions, it is desirable that the component molecules include a polymeric hydrophobic substance or "ballast" group. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups having from 8 to 40 carbon atoms. Representative substituents on such groups are
Alkyl, aryl, typically having from 1 to 40 carbon atoms,
Includes alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamide, carbonyl, alkylsulfonyl, arylsulfonyl, sulfonamide, and sulfamoyl groups. This substituent can also be further substituted.

The photographic elements can be single color elements or multicolor elements. Multicolor elements contain dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element (including the image-forming layer units) can be arranged in a wide variety of orders as known in the art. In certain alternative arrangements, the emulsions sensitive to each of the three primary regions of the spectrum can be dispersed as a single segmented layer.

A typical multicolor photographic element is a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having at least one associated cyan dye-forming coupler, at least one associated magenta dye. A magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having a forming coupler and a yellow comprising at least one blue-sensitive silver halide emulsion layer having at least one associated yellow dye-forming coupler Consists of a support carrying the dye image-forming units. The element can include additional layers such as filter layers, interlayers, overcoat layers, undercoat layers, and the like.

If necessary, the photographic element isResearch D
isclosure, Item 34390, November 1992, (Kenneth Mason
Publication Ltd., Dudley Annex, 12a North Street,
Published by Emsworth, Hampshire PO10 7DQ, England
Used in related magnetic layer applications as described in
You can also. Suitable for use in the emulsions and photographic elements of the present invention.
In the following discussion of the sharp material,Research Disclosure
, Item 308119, December 1989 (sold by the above publishers)
(Hereinafter referred to as "Research Disclosure")
refer. Research Disclosure content (see there
Patents and publications).
And the contents of this specification. Sections referred to hereafter
Refers to the Research Disclosure section.

The silver halide emulsion used in the present invention can be either a negative type or a positive type. Suitable emulsions and their preparation and chemical and spectral sensitization are described in Sections I-IV.
Color materials and development modifiers are provided in sections V and X
XI. Vehicles are described in Section IX and include optical brighteners, antifoggants, stabilizers,
Various additives such as light absorbing and scattering materials, curing agents, coating aids, plasticizers, lubricants, and matting agents are described, for example, in Sections V, VI, VIII, X, XI, XI.
I and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports are described in Sections XIII and XVII, processing methods and agents are described in Sections XIX and XX, and exposure means are described in Section XVIII.

[0045] Coupling leaving groups are well known in the art. These groups determine the equivalent weight of the coupler (ie, whether it is a two- or four-equivalent coupler) or alter the reactivity of the coupler. After those groups have been released from the coupler, the coupler is coated by performing actions such as dye formation, hue control, development acceleration or development inhibition, bleach acceleration or bleach inhibition, electron transfer enhancement, color correction, etc. Layers, or other layers of the photographic recording material, can have advantageous effects.

The presence of hydrogen at the coupling position results in a four-equivalent coupler, and the presence of another coupling-off group results in a two-equivalent coupler. Representative classes of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocycle, sulfonamide, mercaptotetrazole, benzothiazole, mercaptopropionic acid , Phosphonyloxy, arylthio, and arylazo. These coupling-off groups are described in the art, for example, in US Pat. No. 2,455,455.
No. 169, No. 3,227,551, No. 3,432,5
No. 21, 3,476,563, 3,617,29
No. 1, 3,880,661, 4,052,212
Nos. 4,134,766, and British Patent Nos. 1,466,728, 1,531,927, 1,533,039, and British Patent Application Publication No. 2,0.
Nos. 06755 and 2,017,704 (the disclosures of which are incorporated herein by reference).

US Pat. Nos. 4,301,235;
It is effective to use in combination with any known ballast or coupler of a coupling-off group as described in US Pat. Nos. 853,319 and 4,351,897. European Patent No. 213,490, JP-A-58-172647, U.S. Pat. No. 2,983,608
, German Patent No. 2,706,117, British Patent No. 1,530,272, Japanese Patent Application No. A-1139.
No. 35, U.S. Pat. Nos. 4,070,191 and
273,861 and German Patent 2,643,9
As described in US Pat. No. 65/65, couplers can also be used with “opposite” color couplers (eg, to adjust interlayer correction levels), and with masking couplers, It can be used in color negative applications. The masking coupler can be moved or protected.

For example, the coupler combinations of the present invention can include the case where all or part of the yellow coupler is replaced in a color negative photographic element having the following upper to lower layers on a support. (1) One or more overcoat layers containing one or more ultraviolet absorbers (2) Two-layer yellow pack High-sensitivity yellow layer containing "coupler 1": "coupler 1"; benzoic acid, 4-chloro- 3-((2-
(4-ethoxy-2,5-dioxo-3- (phenylmethyl) -1-imidazolidinyl) -3- (4-methoxyphenyl) -1,3-dioxopropyl) amino)-,
Low-sensitive yellow layer containing the same compound together with dodecyl ester, "coupler 2" and "coupler 3": "coupler 2"; propanoic acid, 2-[[5-[[4-
[2-[[[2,4-bis (1,1-dimethylpropyl) phenoxy] acetyl] amino] -5-[(2
2,3,3,4,4,4-heptafluoro-1-oxobutyl) amino] -4-hydroxyphenoxy] -2,
3-dihydroxy-6-[(propylamino) carbonyl] phenyl] thio] -1,3,4-thiadiazole-
2-yl] thio]-, methyl ester "coupler 3"; 1-((dodecyloxy) carbonyl) ethyl (3-chloro-4-((3- (2-chloro-
4-((1-tridecanoylethoxy) carbonyl) anilino) -3-oxo-2-((4) (5) (6)-
(Phenoxycarbonyl) -1H-benzotriazol-1-yl) propanoyl) amino)) benzoate.

(3) An intermediate layer containing fine metallic silver. (4) Three-layer magenta pack “coupler 4”, “coupler 5”, “coupler 6”,
High-sensitivity magenta layer containing “coupler 7” and “coupler 8”: “coupler 4”; benzamide, 3-((2- (2,4
-Bis (1,1-dimethylpropyl) phenoxy) -1
-Oxobutyl) amino) -N- (4,5-dihydro-
5-oxo-1- (2,4,6-trichlorophenyl)
-1H-pyrazol-3-yl)-, "coupler 5"; bezamide, 3-((2- (2,4-
Bis (1,1-dimethylpropyl) phenoxy) -1-
(Oxobutyl) amino) -N- (4 ′, 5′-dihydro-5′-oxo-1 ′-(2,4,6-trichlorophenyl) (1,4′-bi-1H-pyrazole) -3′- Yl)-, "coupler 6"; carbamic acid, (6-(((3- (dodecyloxy) propyl) amino) carbonyl) -5-
Hydroxy-1-naphthalenyl)-, 2-methylpropyl ester, "coupler 7"; acetic acid, ((2-((3-(((3-
(Dodecyloxy) propyl) amino) carbonyl)-
4-hydroxy-8-(((2-methylpropoxy) carbonyl) amino) -1-naphthalenyl) oxy) ethyl) thio)-, "coupler 8"; bezamide, 3-((2- (2,4-
Bis (1,1-dimethylpropyl) phenoxy) -1-
Oxobutyl) amino) -N- (4,5-dihydro-4
-((4-methoxyphenyl) azo) -5-oxo-1
-(2,4,6-trichlorophenyl) -1H-pyrazol-3-yl)-, a medium-sensitivity magenta layer containing "coupler 9": "coupler 9"; 2-propenoic acid in a weight ratio of 1: 1: 2 Butyl ester, styrene, and N- [1- (2,4,
6-trichlorophenyl) -4,5-dihydro-5-oxo-1H-pyrazol-3-yl] -2-methyl-2
A ternary copolymer containing propenamide, a low-sensitivity magenta layer containing "coupler 10": "coupler 10"; tetradecaneamide, N- (4-chloro-3-((4-((4-((2,2 -Dimethyl-1
-Oxopropyl) amino) phenyl) azo) -4,5
-Dihydro-5-oxo-1- (2,4,6-trichlorophenyl) -1H-pyrazol-3-yl) amino)
Phenyl)-is added to couplers 3 and 8.

(5) Intermediate layer (6) Highly sensitive cyan layer containing couplers 6 and 7, coupler 6 and "coupler 11"; 2,7-naphthalenedisulfonic acid, 5- (acetylamino) -3-((4 −
(2-((3-(((3- (2,4-bis (1,1-dimethylpropyl) phenoxy) propyl) amino) carbonyl) -4-hydroxy-1-naphthalenyl) oxy) ethoxy) phenyl) azo ) -4-Hydroxy-,
A three-layer cyan pack having a medium-speed cyan layer containing a disodium salt and a low-speed cyan layer containing couplers 2 and 6; (7) an undercoat layer containing a coupler 8; and (8) an antihalation layer. (Eg bleaching or fixing)
Can be used in combination with a material that promotes or modifies image quality to improve image quality. European Patent 193,389
No. 301,477, U.S. Pat. No. 4,163,66
No. 9, No. 4,865,956 and No. 4,923,7
Bleach accelerator releasing couplers such as those described in US Pat. Nucleating agents, development accelerators or their precursors (British Patent Nos. 2,097,140 and 2,131,188), electron transfer agents (U.S. Pat. Nos. 4,859,578, 4,912,025), hydroquinones, aminophenols, amines, antifoggants and color-mixing inhibitors such as derivatives of gallic acid, catechol, ascorbic acid, hydrazides, sulfonamidophenols, and It is also conceivable to use the composition together with a non-color-forming coupler.

The composition of the present invention is used as an oil-in-water dispersion, a latex dispersion or a solid particle dispersion, together with a colloidal silver sol or a filter dye layer comprising a yellow and / or magenta filter dye. You can also. In addition, they have been described as "smearing" couplers (see, for example, U.S. Pat.
66,237; EP 96,570; U.S. Pat. Nos. 4,420,556 and 4,543,323.
(As described in each of the above-mentioned specifications). Further, the above composition is prepared, for example, in Japanese Patent Application No.
1-258249 or U.S. Pat. No. 5,019,49.
It can also be blocked or applied in protected form as described in US Pat.

In addition, the compositions can be used in combination with an image modifying compound such as a "development inhibitor releasing" compound (DIR). Development inhibitor releasing compounds useful in connection with the compositions of the present invention are known in the art, and examples thereof are disclosed in US Pat. No. 3,137,5.
No. 78, No. 3,148,022, No. 3,148,06
No. 2, 3,227,554, 3,384,657
Nos. 3,379,529 and 3,615,506
Nos. 3,617,291 and 3,620,746
Nos. 3,701,783, 3,733,201
No. 4,049,455 and 4,095,984
Nos. 4,126,459 and 4,149,886
No. 4,150,228 and 4,211,562
No. 4,248,962 and 4,259,437
Nos. 4,362,878 and 4,409,323
Nos. 4,477,563 and 4,782,012
No. 4,962,018 and 4,500,634
Nos. 4,579,816 and 4,607,004
Nos. 4,618,571 and 4,678,739
Nos. 4,746,600 and 4,746,601
Nos. 4,791,049 and 4,857,447
Nos. 4,865,959 and 4,880,342
Nos. 4,886,736 and 4,937,179
Nos. 4,946,767 and 4,948,716
Nos. 4,952,485 and 4,956,269
Nos. 4,959,299 and 4,966,835
No. 4,985,336 and British Patent 1,5.
Nos. 60,240, 2,007,662, 2,03
2,914, 2,099,167, German Patent Nos. 2,842,063, 2,937,127, 3,636,824, 3,644,416, and the following. European Patent Nos. 272,573 and 335,31
No. 9, 336, 411, 346, 899, 3
62,870, 365,252, 365,34
No. 6, No. 373, 382, No. 376, 212, No. 3
77,463, 378,236, 384,67
0, 396,486, 401,612, 4
No. 01,613.

These compounds are also available from Photographic Sci.
ence and Engineering , Vol.13, p.174 (1969) CRBar
r, JRThirtle and PWVittum, "Development Inhibitor Emitting Couplers for Color Photography" (incorporated herein by reference). Generally, development inhibitor releasing (DIR) couplers comprise a coupler component and an inhibitor coupling off component (IN). Development inhibitor releasing couplers are time delayed (DIA) which also include a chemical switch to delay the release of the timing component or inhibitor.
R coupler). Typical inhibitor components are: oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, Isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptooxazoles , Mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, mercapto Oxa benzothiazoles, tellurocarbonyl tetrazole (Telleurot
etrazoles) or benzoisodiazoles. In a preferred embodiment, the inhibitor component or group has the formula:

[0054]

Embedded image

Wherein R _I is selected from the group consisting of straight-chain and branched alkyl, benzyl and phenyl groups having 1 to 8 carbon atoms, and those groups have an alkoxy substituent. _II is selected from R _I and -SR _I, R _III is an alkyl group having a linear or branched carbon atoms from 1 to about 5, m is 1 to 3, and, R _IV Is hydrogen, halogen and alkoxy, phenyl and carbon amide groups, -COOR _V and -NH
COOR _V and R _V is selected from substituted and unsubstituted alkyl and aryl groups).

The coupler component typically included in a development inhibitor releasing coupler produces the corresponding image dye in the layer in which it is present, but may also produce another color as associated with a different film layer. it can. It is also effective that the coupler component contained in the development inhibitor releasing coupler produces colorless products and / or products that wash away the photographic material during processing (so-called "universal" couplers).

As described above, the development inhibitor releasing couplers are based on groups which use a cleavage reaction of hemiacetal (US Pat. No. 4,146,396, Japanese Patent Application Nos. 60-249148 and 60-249149). ), A group using an intramolecular nucleophilic substitution reaction (U.S. Pat. No. 4,248,962), and a group using an electron transfer reaction along a conjugated system (U.S. Pat. Nos. 4,409,323 and 4,100). 421,845
No., Japanese Patent Application No. 57-188035 and No. 58-98728
Nos. 58-209736 and 58-209736), groups using ester hydrolysis (German Patent Application (OLS) No. 2,626,315), groups using cleavage reaction of imino ketals (U.S. Pat.
46,073), a group which acts as a coupler or a reducing agent after a coupler reaction (US Pat. No. 4,43,43).
8,193,4,618,571) and groups that combine the above features to produce groups that delay the release of the inhibitor in time. One of the typical timing groups or components is
Of the following formula:

[0058]

Embedded image

Wherein IN is an inhibitor component and Z is nitro, cyano, alkylsulfonyl, sulfamoyl (—SO ₂ NR ₂ ), and sulfonamide (—NRS
Selected from the group consisting of O ₂ R) groups, n is 0 or 1, and R _VI is selected from the group consisting of substituted and unsubstituted alkyl and phenyl groups. 2.) The oxygen atom of each timing group is attached to the coupling-off position of the respective coupler component of the DIAR.

[0060] Suitable development inhibitor releasing couplers for use in the present invention are (but are not limited to):

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

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In the present invention, tabular grain silver halide emulsions are particularly effective. Certain possible tabular grain emulsions have more than 50% of the total projected area of the emulsion grains.
Thickness less than 0.3 μm (0.5 μm for blue-sensitive emulsions)
Thinner thickness) and greater than 25 (preferably 100
(Greater) average tabularity (T). The term "tabularity" is defined in the art as T = ECD / t ² (ECD is the average equivalent circular diameter of tabular grains in microns, and t is the average thickness of the tabular grains in microns. Is).

The average effective ECD of a photographic emulsion can range up to about 10μ, but the ECD values of actual emulsions rarely exceed about 4μ. Since both photographic sensitivity and granularity increase with increasing ECD values,
It is generally preferred to use the smallest tabular grain ECD value that meets the required target sensitivity. Emulsion tabularity increases significantly as tabular grain thickness decreases.
It is generally preferred that the target tabular grain projected area be filled with thin (t <0.2μ) tabular grains. To achieve the lowest level of granularity, it is preferred that the target tabular grain projected area be filled with ultrathin (t <0.06μ) tabular grains. Typically, tabular grain thicknesses range down to about 0.02μ. However, thinner tabular grain thicknesses are also contemplated. For example, Da
Ubendiek et al., in U.S. Pat. No. 4,672,027, report a 3 mol% iodide tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 .mu.m.

As noted above, tabular grains thinner than the specified thickness account for at least 50% of the total grain projected area of the emulsion. In order to maximize the benefits of high tabularity, tabular grains satisfying the stated thickness criteria are conveniently and account for the highest achievable percentage of the total grain projected area of the emulsion. Is preferred. For example, in preferred emulsions, tabular grains satisfying the stated thickness criteria or higher account for at least 70% of total grain projected area.
In the highest performance tabular grain emulsions, tabular grains satisfying the thickness criterion or more account for at least 90% of total grain projected area.

Suitable tabular grains are shown below: Research
Disclosure, Item 22534, December 1983, (Kenneth Ma
son Publication Ltd., Dudley Annex, 12a North Stre
et., Emsworth, Hampshire PO 107DQ, England), U.S. Patent Nos. 4,439,520 and 4,41.
4,310, 4,433,048, 4,64
3,966, 4,647,528 and 4,66
5,012, 4,672,027, 4,67
8,745, 4,693,964, 4,71
No. 3,320, No. 4,722,886, No. 4,75
5,456, 4,775,617 and 4,79
7,354, 4,801,522, 4,80
6,461, 4,835,095, 4,85
No. 3,322, No. 4,914,014, No. 4,96
No. 2,015, No. 4,985,350, No. 5,06
It can be selected from the wide variety of conventional techniques of US Pat. Nos. 1,069 and 5,061,616.

The emulsion can be a surface-sensitive emulsion (that is, an emulsion that mainly forms a latent image on the surface of silver halide grains, or an emulsion that mainly forms an internal latent image inside silver halide grains). Emulsions can be negative-working emulsions, such as surface-sensitive emulsions or fogged internal latent image-forming emulsions, or fogged internal latents which are positive when developed in the presence of a nucleating agent with uniform exposure. It can be an image forming type direct positive emulsion.

The photographic element can be exposed to actinic radiation (typically in the visible region of the spectrum) to produce a latent image, which can then be processed to produce a visible dye image. Processing to produce a visible dye image includes the step of contacting the photographic element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developing agent then reacts with the coupler to form a dye.

In the case of negative-working silver halide, a negative image is formed by the above-mentioned processing steps. 19
1982 British Journal of Photography Annual, page 20
9-211, and 1988 pages 191-198. Developing the exposed silver halide (but not forming a dye) with a non-color developing agent prior to the color developing step to obtain a positive (ie reversal) image;
The photographic element is then uniformly fogged to allow the unexposed silver halide to be developed. Alternatively, a positive image can be obtained using a direct positive emulsion.

Preferred color developing agents are p
-Phenylenediamines: 4-amino-N, N-
Diethylaniline hydrochloride, 4-amino-3methyl-N,
N-diethylaniline hydrochloride, 4-amino-3-methyl-
N-ethyl-N- (b- (methanesulfonamido) ethyl) aniline sesquisulfate hydrate, 4-amino-3methyl-N-ethyl-N- (b-hydroxyethyl) aniline sulfate, 4-amino- 3-b- (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N- (2-methoxyethyl)
-M-toluidine di-p-toluenesulfonic acid.

Normally, after development, normal bleaching, fixing,
Alternatively, a bleaching-fixing step is continued, followed by removal of silver or silver halide, followed by washing and drying steps. By regarding groups containing a substitutable hydrogen (e.g., alkyl, amine, aryl, alkoxy, heterocycle, etc.) as identical, unless otherwise stated, the substituent referred to is only the unsubstituted form of the substituent But also includes forms substituted with any photographically useful substituent. Usually, the substituents have less than 30 carbons, typically less than 20 carbons.

[0074]

The present invention will be described more specifically with reference to the following examples. The formulas of the chemicals used are shown below. Photographic Example 1 A comparative color photographic recording material for color negative development (Photographic Sample 101) was prepared by sequentially applying the following layers to a transparent support of cellulose triacetate. The amount of silver halide, expressed in silver g per 1 m ^2. The amount of other materials, expressed in g per 1 m ^2.

Layer 1: Antihalation Layer Black colloidal silver sol containing 2.44 g gelatin and 0.236 g silver. Layer 2: First (lowest sensitivity) red-sensitive layer 0.22 g of red-sensitized silver iodobromide emulsion [1.3 mol% of iodine, average grain diameter 0.55 µm, average grain thickness 0.08
μ], 0.33 g of red-sensitized silver iodobromide emulsion [4 mol% of iodine, average grain diameter 1.0 μ, average grain thickness 0.09]
μ], 0.56 g of cyan dye image-forming coupler C-
1. 0.089 g of BAR compound B-1, gelatin
83g.

Layer 3: Second (medium-speed) red-sensitive layer 0.56 g of a red-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 1.3μ, average particle thickness 0.12μ], 0.
23 g of cyan dye image-forming coupler C-1, 0.02
2 g of cyan dye-forming masking coupler CM-1,
0.011 g of DIR compound D-2, gelatin 1.66
g.

Layer 4: Third (highest sensitivity) red-sensitive layer 1.22 g of red-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 2.6 μ, average particle thickness 0.13 μ], 0.
18 g of cyan dye image forming coupler C-1, 0.05
0 g of cyan dye-forming masking coupler CM-1,
0.003 g of DIR compound D-6, 0.050 g of D
IR compound D-2, gelatin 1.36 g.

Layer 5: Intermediate layer 0.11 g of yellow dye material YD-1 and 1.33 g of gelatin. Layer 6: First (lowest sensitivity) green-sensitive layer 0.78 g of a green-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 1.0 μ, average particle thickness 0.09 μ], 0.
22 g of magenta dye image-forming coupler M-2, 0.0
89 g of magenta dye image forming coupler M-3, 1.78 g of gelatin.

Layer 7: Second (medium-speed) green-sensitive layer 1.00 g of a green-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 1.25μ, average particle thickness 0.12μ],
0.089 g of magenta dye image-forming coupler M-2,
0.028 g of magenta dye image-forming coupler M-3,
0.089 g of magenta dye forming masking coupler M
M-1, gelatin 1.48 g.

Layer 8: Third (highest sensitivity) green-sensitive layer 1.00 g of a green-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 2.16μ, average particle thickness 0.12μ],
0.089 g of magenta dye image-forming coupler M-2,
0.028 g of magenta dye image-forming coupler M-3,
0.044 g of magenta dye-forming masking coupler M
M-1, 0.008 g of DIR compound D-3, 0.00
8 g of DIR compound D-4, 1.33 g of gelatin.

Layer 9: Intermediate layer 0.11 g of yellow dye material YD-2, gelatin 1.
33 g. Layer 10: First (low-sensitivity) blue-sensitive layer 0.11 g of blue-sensitized silver iodobromide emulsion [1.3 mol% of iodine, average grain diameter 0.55 µm, average grain thickness 0.08
μ], blue-sensitized silver iodobromide emulsion 0.26 g [iodine 4 mol%, average grain diameter 1.25 μ, average grain thickness 0.12
μ], blue-sensitized silver iodobromide emulsion 0.26 g [iodine 6 mol%, average grain diameter 1.0 μ, average grain thickness 0.26
μ], 0.94 g of yellow dye image-forming coupler Y-
2, 0.049 g of DIR compound D-5, 0.003 g
BAR compound B-1, 2.6 g of gelatin.

Layer 11: Second (highly sensitive) blue-sensitive layer 0.39 g of blue-sensitized silver iodobromide emulsion [4 mol% of iodine,
Yellow dye image-forming coupler having an average grain diameter of 3.0 μm, an average grain thickness of 0.14 μm, a blue-sensitized silver iodobromide emulsion 0.39 g [iodine 9 mol%, average grain diameter 1.0], 0.28 g Y-2, 0.044 g of DIR compound D-5,
0.006 g of BAR compound B-1, gelatin 1.97
g.

Layer 12: protective layer 1 0.106 g of dye UV-1, 0.106 g of dye UV
-2, non-sensitized silver bromide Lippman emulsion 0.222 g, gelatin 2.03 g. This film was cured with 2% by weight of the total gelatin of hardener H-
1 was applied and cured. Surfactants, coating aids, scavengers, soluble absorbent dyes and stabilizers were added to the various layers of this sample as commonly practiced in the art.

A photographic recording material sample 102 was prepared in the same manner as photographic sample 101, except that 0.011 g of DIR compound D-4 was added to layer 7. Photographic recording material sump
Layer 103 and DIR compound D-4 in layer 7 at 0.022 g.
Except for adding, it was prepared in the same manner as in photo sample 101. Photographic recording material sample 104 was prepared using DIR compound D-
Except for adding 0.009 g of Compound No. 1 to Layer 7, it was prepared in the same manner as in Photo Sample 101.

A photographic recording material sample 105 was prepared in the same manner as the photographic sample 101, except that 0.018 g of the DIR compound D-1 was added to the layer 7. Photographic recording material sump
Le 106, 0.027 g of DIR compound D-1 to layer 7
Except for adding, it was prepared in the same manner as in photo sample 101.

[0086]

[Table 3]

A) Rr / Rn-red separation gamma divided by red neutral gamma. b) Gg / Gn-Green separation gamma divided by green neutral gamma. c) Bb / Bn-blue separation gamma divided by blue neutral gamma. Looking at the main part of the data, it can be seen that neutral exposure is causing exposure and development of adjacent color records. This, in turn, can release to the adjacent record an inhibitor that can move to the associated record, thereby suppressing the development of the associated layer. Thus, the gamma of the associated color is suppressed. By comparison, exposing a photographic element to a single color that affects only one type of color record does not result in release of the inhibitor in adjacent records. Therefore, monochromatic exposure
Represents a mode that is unsuppressed from an inter-image perspective. If not suppressed, the ratio would be one. As the suppression increases due to the inter-image effect, the ratio increases as the neutral gamma decreases.

As shown by the photographic data in Table III, the weakest inhibitor DIR compound D-4 was added to the fastest green sensitive layer.
And the photographic sample incorporating the same weak DIR compound in the low sensitivity layer shows increased inhibition of red recording without significantly increasing inhibition of blue recording. This combination does not achieve the desired suppression effect on blue recording. On the other hand, a photographic sample incorporating the strong inhibitor DIR with the timing group, compound D-1, in the low sensitivity layer has the effect of increasing blue suppression as a result of green exposure while maintaining red suppression. . This is the desired purpose.

Photographic Example 2 A color photographic recording material (photographic sample 102) for color negative development was applied to a cellulose triacetate transparent support in order.
It was prepared by applying the following layers. The amount of silver halide, expressed in silver g per 1 m ^2. The amount of other materials, expressed in g per 1 m ^2.

Layer 1: Antihalation Layer Black colloidal silver sol containing 2.44 g gelatin and 0.236 g silver. Layer 2: First (lowest sensitivity) red-sensitive layer 0.49 g of red-sensitized silver iodobromide emulsion [1.3 mol% of iodine, average grain diameter 0.55 µm, average grain thickness 0.08
μ], 0.48 g of a red-sensitized silver iodobromide emulsion [4 mol% of iodine, average grain diameter 1.0 μ, average grain thickness 0.09]
μ], 0.56 g of cyan dye image-forming coupler C-
1. 0.033 g of cyan dye-forming masking coupler CM-1, 0.039 g of BAR compound B-1, 1.83 g of gelatin.

Layer 3: Second (medium-speed) red-sensitive layer 0.72 g of red-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 1.3μ, average particle thickness 0.12μ], 0.
23 g of cyan dye image-forming coupler C-1, 0.02
2 g of cyan dye-forming masking coupler CM-1,
0.011 g of DIR compound D-1, gelatin 1.66
g.

Layer 4: Third (highest sensitivity) red-sensitive layer 1.11 g of a red-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 2.6 μ, average particle thickness 0.13 μ], 0.
13 g of cyan dye image forming coupler C-1, 0.03
3 g of cyan dye-forming masking coupler CM-1,
0.024 g of DIR compound D-1, 0.050 g of D
IR compound D-2, gelatin 1.36 g.

Layer 5: Intermediate layer 0.11 g of yellow dye material YD-1 and 1.33 g of gelatin. Layer 6: First (lowest sensitivity) green-sensitive layer 0.62 g of green-sensitized silver iodobromide emulsion [1.3 mol% of iodine, average grain diameter 0.55 µm, average grain thickness 0.08
μ], green sensitized silver iodobromide emulsion 0.32 g [iodine 4 mol%, average grain diameter 1.0 μ, average grain thickness 0.09
μ], 0.24 g of magenta dye image-forming coupler M-
1. 0.067 g of magenta dye forming masking coupler MM-1, 1.78 g of gelatin.

Layer 7: Second (medium) green-sensitive layer 1.00 g of a green-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 1.25μ, average particle thickness 0.12μ],
0.091 g of magenta dye image-forming coupler M-1,
0.067 g of magenta dye forming masking coupler M
M-1, 0.024 g of DIR compound D-1, gelatin 1.48 g.

Layer 8: Third (highest sensitivity) green-sensitive layer 1.00 g of a green-sensitized silver iodobromide emulsion [4 mol% of iodine,
Average particle diameter 2.16μ, average particle thickness 0.12μ],
0.072 g of magenta dye image-forming coupler M-1,
0.056 g of magenta dye-forming masking coupler M
M-1, 0.01 g of DIR compound D-3, 0.011
g of DIR compound D-4, 1.33 g of gelatin.

Layer 9: Intermediate layer 0.11 g of yellow dye material YD-2, gelatin 1.
33 g. Layer 10: first (low-sensitivity) blue-sensitive layer 0.24 g of blue-sensitized silver iodobromide emulsion [1.3 mol% of iodine, average grain diameter 0.55 μm, average grain thickness 0.8 μm],
0.61 g of blue sensitized silver iodobromide emulsion [6 mol% of iodine,
Average particle diameter 1.0 μ, average particle thickness 0.26 μ], 0.
29 g of yellow dye image-forming coupler Y-1, 0.7
2 g of yellow dye image forming coupler Y-2, 0.01
7 g of cyan dye image forming coupler C-1, 0.067
g DIR compound D-5, 0.003 g BAR compound B-1, 2.6 g gelatin.

Layer 11: Second (highly sensitive) blue-sensitive layer 0.23 g of blue-sensitized silver iodobromide emulsion [4 mol% of iodine,
Yellow dye image-forming coupler having an average grain diameter of 3.0 μm, an average grain thickness of 0.14 μm, a blue-sensitized silver iodobromide emulsion 0.59 g [iodine 9 mol%, average grain diameter 1.0] and 0.090 g Y-1, 0.23 g of yellow dye image forming coupler Y-2, 0.022 g of cyan dye image forming coupler C-1, 0.05 g of DIR compound D-5, 0.1 g of DIR compound D-5.
006 g of BAR compound B-1, 1.97 g of gelatin.

Layer 12: protective layer 0.111 g of dye UV-1, 0.111 g of dye UV
-2, non-sensitized silver bromide Lippman emulsion 0.222 g, gelatin 2.03 g. This film was cured with 2% by weight of the total gelatin of hardener H-
1 was applied and cured. Surfactants, coating aids, scavengers, soluble absorbent dyes and stabilizers were added to the various layers of this sample as commonly practiced in the art.

The photographic recording material sample 108 was
Prepared similarly to Photographic Sample 107 except that it had 0.028 g of the magenta dye forming masking coupler.
The photographic recording material sample 109 was coated with 0.033 g of the layer 7.
Was prepared in the same manner as in Photographic Sample 107, except that it had Photo recording materials
Charge sample 110 was prepared similarly to photographic sample 101 except that layer 6 had 0.033 g of the magenta dye forming masking coupler.

The performance of this combination with the couplers of the present invention to provide the desired effect in the blue sensitive layer was tested to determine the effect with and without the yellow colored magenta masking coupler.
The results are shown in Table IV.

[0101]

[Table 4]

A) Low Bb / Bn: The blue separation gamma divided by the blue neutral gamma between the Dmin + 0.15 density and the point 0.4 log E below this point. b) Medium Bb / Bn: Dmin + 0.45 of 0.15 concentration
ogE low point and 1.1 log of Dmin + 0.15 concentration
E The blue separation gamma between the low point and the blue neutral gamma divided by the blue neutral gamma.

C) Middle upper part Bb / Bn: Dmin + 0.1
The blue separation gamma divided by the blue neutral gamma between the 1.1 log E low point at 5 densities and the 1.8 log E low point at Dmin + 0.15 density. * H: high sensitivity, M: medium sensitivity, L: low sensitivity, as demonstrated by the data shown in Table IV, with the DIR couplers of the present invention and with the highest, middle and lowest sensitivity green-sensitive halogenation By arranging the masking coupler in the silver layer, the interimage effect of suppressing blue as a result of green exposure can be controlled over a desired exposure region, and color rendering can be improved.

Considering all the data, it can be seen that a yellow dye-forming DIR coupler, such as D-4, which does not have a timing group that releases a weak inhibitor fragment, is used in the fast green-sensitive silver halide emulsion layer to form a red dye. A cyan dye forming DIR with controlled timing, having a timing group and containing a strong inhibitor fragment, such as D-1
It is evident that couplers can be used in slow green sensitive silver halide emulsion layers to control blue suppression. In addition, masking couplers such as MM-1 can be placed in one or more green-sensitive silver halide emulsion layers to balance blue interimage suppression as a result of green exposure over the desired exposure area. it can.

The formula of the compound used is shown below:

[0106]

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[0107]

Embedded image

[0108]

Embedded image

[0109]

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[0110]

Embedded image

[0111]

Embedded image

[0112]

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[0113]

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Other preferred embodiments of the present invention are described below in connection with the claims. (Aspect 1) A DIR containing a weak inhibitor has the following formula:

[0115]

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A photographic element according to claim 1 having an inhibitor fragment having a structure selected from: (Aspect 2) A DIR containing a strong inhibitor has the following formula:

[0117]

Embedded image

The photographic element of claim 1 having an inhibitor fragment selected from the group consisting of: (Embodiment 3) The photographic element according to claim 1, wherein the DIR having a timing group contains a quinone methide timing group. (Embodiment 4) The photographic element according to claim 1, wherein the yellow dye-forming coupler is an open-chain ketomethylene compound.

(Aspect 5) The cyan dye-forming coupler is a phenolic or naphthol compound.
The photographic element described in. (Embodiment 6) The photographic element of claim 1, wherein the photographic element comprises at least three layers sensitized to green light and having different sensitivities. (Embodiment 7) The photographic element according to embodiment 4, wherein the yellow dye-forming coupler is contained in the fastest layer.

(Embodiment 8) The photographic element according to embodiment 5, wherein the cyan dye-forming coupler is contained in the medium-speed layer. (Embodiment 9) The photographic element of claim 1, wherein the yellow colored magenta dye-forming masking coupler is contained in at least one of the green-sensitive layers consisting of at least three layers having different sensitivities.

(Embodiment 10) The masking coupler has the following formula:

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

The photographic element according to embodiment 9, which is selected from the group consisting of: (Embodiment 11) A photographic element according to embodiment 9, wherein all of the green-sensitive layers comprising at least three layers having different sensitivities include the masking coupler according to embodiment 10. (Embodiment 12) The amount of the masking coupler according to embodiment 10 in a green-sensitive layer consisting of at least three layers having different sensitivities is substantially equivalent to the photographic element to green light over the photosensitive range of the green-sensitive layer. The photographic element of embodiment 11, which is an amount sufficient to provide a linear response to the photographic element.

(Aspect 13) A method for producing an image from a photographic element according to claim 1, comprising contacting the exposed photographic element with a color developing agent. (Aspect 14) The method according to Aspect 13, wherein the developing agent is phenylenediamine.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/305 G03C 7/20

Claims (3)

(57) [Claims] A yellow sensitized to green light and comprising at least two photosensitive silver halide layers having different sensitivities and releasing a development inhibitor having a weak inhibitor fragment in the associated sensitive layer. A photographic element comprising a dye-forming DIR coupler and further comprising a cyan dye-forming DIR coupler having a timing group containing a strong inhibitor fragment that releases a precursor of the development inhibitor fragment in the associated slower layer. 2. The photographic element according to claim 1, wherein the weak inhibitor fragment is selected from the group consisting of benzotriazole and alkylmercaptotetrazole. 3. The photographic element according to claim 2, wherein the strong inhibitor fragment is phenylmercaptotetrazole.